Monoazo indandione containing dyestuffs



United States Patent 3,270,002 MONOAZO INDANDIONE CONTAINING DYESTUFFSErnest Marian, Bottrningen, Basel-Land, and Otto Senn, Arlesheim,Basel-Land, Switzerland, assignors to Sandoz Ltd. (also known as SandozAG.), Basel, Switzerland No Drawing. Filed Aug. 3, 1962, Ser. No.214,524 Claims priority, application Switzerland, June 22, 1959, 75,044;Nov. 18, 1959, 80,755 1 Claim. ((31. 260193) The present application isa continuation-in-part of copending application Serial No. 34,388, filedJune 7, 1960 (now US. Patent No. 3,153,643).

The present invention relates to indandione dyestufis of the formula xrepresents a member selected from the group consisting of chlorine andbromine,

y represents a member selected from the group consisting of hydrogen,chlorine and bromine,

z represents a member selected from the group consisting of chlorine,bromine, nitro and cyano,

w represents a member selected from the group consisting of chlorine,bromine and cyano,

n is one of the integers 1 and 2,

and the nucleus A is a member selected from the group consisting ofphenylene, S-chlorophenylene and 5,6-dichlorophenylene.

The process for the production of dyestuffs I consists in coupling 1 molof the diazo compound of an amine of the formula B--NH (III) with 1 molof a 1,3-indandione which may contain non water-solubilizingsubstituents in the phenylene nucleus or with 1 mol of a compound whichis converted into a 1,3-indandione under the operating conditionsemployed.

The coupling reaction is effected in acid, neutral or alkaline medium atlow temperatures, e.g. 5 to C.

Diazo components which are worth special mention as amines of Formula111 are:

l-amino-Z-chloroor -bromo-4-nitro-benzene, 1-amino-2,6-dichloroor-dibromo-4-nitro-benzene, l-amino-2,5 dichloroor-dibromo-4-nitro-benzene, 1-amino-2-chloroor -bromo-4,6-dinitro-benzene,1-amino-2-cyano-4-nitrobenzene, 1-amino-2-cyano-6-chloroor -bromo-4-nitro-benzene.

Examples of suitable coupling components, other than 1,3-indandioneitself, are monochloro-1,3-indandione, 5,6-dichloro-1,3-indandione,2-substituted indandiones which under the conditions of applicationexchange their radical in the 2-position for a phenylazo radical, e.g.1,3-indandione-Z-carboxylic acid and its alkyl esters.

The indandione dyestuffs are brought into a finely divided form bydissolving in a water-miscible solvent, if necessary at elevatedtemperature, and running the 3,270,002 Patented August 30, 1966 solutioninto water, upon which the product is filtered off, washed and kneadedwith a dispersing agent. The paste formed can be dried at normal orreduced pressure or by nozzle drying. Another method of converting thedyestuffs into a finely divided form is to grind or knead them in thedry or moist state in presence of dispersing agents and if necessaryfillers and/or grinding assistants to reduce the particle size, thedyestuff then being dried by one of the drying processes employed inpigment manufacture. The dyestuff preparations thus obtained contain theindandione dyestuffs in particles of the order of magnitude of Lu.

In certain cases the affinity of the dyestuff preparations can beimproved by mixing two or more dyestuffs which have been converted intothe finely divided form.

The indandione dyestuffs disclosed herein are suitable for dyeing,padding and printing polyester fibers, in particular the condensationproducts of terephthalic acid and ethylene glycol which are marketedunder the trade names Dacron, Dacron 64, Terylene, Tergal, Terital,Trevira, Kodel, Teron, Fortrel, Vycron, Lanon and Diolen; further thecellulose ester fibers: secondary cellulose acetate and cellulosetriacetate; and the synthetic polyamide fibers (nylon 66 and the typesmarketed under the trade names Perlon, Mirlon, Grilon and Rilsan).

The yellow to orange dyeings, paddings and prints obtained on polyesterfibers are notable for their good fastness to light, sublimation andheat setting and their very good washing and perspiration fastness. Thedyestuffs reserve wool, cotton and viscose in blended fabrics. Thislast-mentioned property has become very important as a result of thewide variety of blended fabrics now produced, especially those composedof a polyester fiber and wool. When blended fabrics of this type aredyed with disperse dyestuffs the wool is stained to a considerable depthand as the stain is not fast the goods lose in value. There are nocommercially available yellow disperse dyestuffs which give asufficiently good reserve of wool. A number of the indandione dyestuffsof the present invention are superior to all the known commercialdyestuffs in this respect.

An other advantage of the new dyestuffs is their excellent stabilityagainst hydrolysis in water up to C. and in the dry state up to 250 C.Most of the greenish yellow dyestuffs of shade are more or lessdecomposed when dyed under pressure and/or at higher pH-values. The newdyestuffs are therefore useful for dyeing polyester fibers at the boilin presence of carriers in a wide pH-range, under pressure up to 150 C.and by the Ther mos-ol Process when fixed at 180-230 C.

The dyeings on secondary cellulose acetate and cellulose triacetate havevery nearly the same shade as those on polyester fibers and, further,they show good fastness to pleating and gas fumes and are readilydischargeable.

The dyeings on synthetic polyamide fibers are notable for their good toexcellent fastness to washing.

In the following examples the parts and percentages are by Weight andthe temperatures in degrees centigrade.

Example 1 17.25 parts of 1-amino-Z-chloro-4-nitrobenzene are diazotizedin the normal way with 25 parts of 30% hydrochloric acid and 6.9 partsof sodium nitrite. Meanwhile 14.5 parts of 1,3-indandione are dissolvedin 200 parts of water and 8 parts of 30% sodium hydroxide solution sothat the solution reacts weakly alkaline: this solution is cooled to 0and the diazo compound is run into it simultaneously with 250 parts of a10% solution of sodium carbonate. On completion of coupling theprecipitated dyestuff is filtered off, washed with water and dried. Itis obtained as yellow powder which dissolves in concentrated 3 sulfuricacid to give orange solutions; on purification from alcohol its meltingpoint is 260-263 A dyeing preparation is prepared by grinding 1 part ofthe above dyestuff with 1 part of sodium dinaphthylmethanedisulfonateand 8 parts of water in a ball mill and, drying the resulting paste in aspray drier.

3 parts of this dyestuff preparation of the above dyestuff are pastedwith a little cold soft water. Cold soft water is run onto the paste andthe dispersion well stirred and added through a sieve to a dyebath of 2parts of lauryl alcohol sulfonate and 4000 parts of water.

100 parts of a scoured fabric of the polyester fiber Dacron (registredtrademark) are entered in the dyebath at 40-50". The temperature isslowly increased and dyeing continued in presence of 20 parts of anemulsion of a chlorinated benzene in water for 1 to 2 hours at 95- 100.The fabric is then rinsed, soaped, rinsed again and dried. It is dyed ayellow shade which is fast to sub- .limation and heat setting. Woolpresent in the dyebath is reserved. The yellow dyeing also possessesgood fastness to light, cross dyeing, washing, water, seat water,perspiration and gas fumes and is dischargeable white.

The chlorinated benzene can be replaced by parts of2-hydroxy-1,1'-diphenyl or the dyeing carried out without a carrier at120 in 30 minutes under pressure.

Example 2 The dyestuff described in Example 1 can also be obtained asfollows: 21.4 parts of the sodium salt of 1,3- indandione-carboxylicacid ethyl ester are dissolved by boiling for the a short time in 300parts of acetone with the addition of 300 parts of concentratedhydrochloric acid. The yellow solution formed is cooled to and coupledwith the diazo solution prepared as described in Example 1. Theprecipitated dyestutf is filtered, washed and dried.

In the table below details are given of further examples of indandionedyestuifs which can be produced by the operating procedures of Examples1 and 2. The diazo component has the general formula In columns 2, 3 and4 the substituents x, y and z are listed, in column 4 the couplingcomponents and in column 5 the uncorrected melting point of theindandione dyestuffs.

All the dyestuffs listed give on Dacron yellow dyeings with similarproperties.

Example :1: y Coupling Melting Component Point, deg.

mmmmmmmm 5,6-dichlor0-1,3-

indandione.

Further useful dyestuffs according to the invention are the following:

2-( 2,5'-dichloro-4-nitrophenylazo -1,3-indandione,

2-(2'-chloro-4-nitrophenylazo)-5-chloro-1,3-indandione and2-(2'-cyano-4'-nitrophenylazo)-5-chloro-1,3-indandione.

Formulae of representative dyes of the foregoing examples are asfollows:

Examples 1 and 2 0 II I 011 0 ll 7 0 Example 6 0 II i O 2N- N=N C H N02(I? 0 Example 7 i r & O,N N=N CH O Having thus disclosed the inventionwhat we claim is: The indandione dye of the formula References Cited bythe Examiner UNITED STATES PATENTS 1,075,305 10/1913 Schmidt 260l932,339,739 1/1944 Blackshaw et al. 81 2,658,889 11/1953 Goldberg et a1260193 2,782,189 2/ 1957 Merian 260207.5 2,891,942 6/1959 Merian 2601572,918,344 12/1959 Jenny 839 3,093,437 6/1963 Merian et al 260-193FOREIGN PATENTS 692,648 6/ 1940 Germany.

CHARLES B. PARKER, Primary Examiner.

NORMA S. MILESTONE, REYNOLD I. FINNEGAN,

DONALD M. PAPUGA, Assistant Examiners.

